JP3086272B2 - Organic electroluminescence device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescence device, and more particularly, to an organic electroluminescence device which improves light emission uniformity and suppresses a decrease in initial luminance.

[0001]

2. Description of the Related Art Electroluminescent devices (EL devices) are self-luminous, have high visibility, are completely solid devices, and have excellent impact resistance. Therefore, various devices using inorganic / organic compounds have been proposed and put to practical use. Among these elements, the organic EL element can greatly reduce the applied voltage, and therefore various materials and elements are being developed. With respect to the configuration of the organic EL element, a configuration is known in which a hole injection layer and an electron injection layer are provided as necessary for improving light emission performance, based on an anode / light emitting layer / cathode. In such an element configuration, the cathode must have sufficient adhesion to the light emitting layer. If the adhesiveness is not sufficient, the mechanical strength is reduced, and non-uniformity is generated. Further, the load in the light emitting surface becomes non-uniform, which promotes deterioration and shortens the life, which is a problem for practical use.

Conventionally, there is known a technique in which an electron injection layer and a hole blocking layer are provided between a light emitting layer and a cathode as required. In particular, when providing the latter layer, these techniques are determined by the difference in energy level from the light emitting layer,
The material must follow this concept. For example, "a hole blocking layer (hole blocking layer) having a first oxidation potential greater than the first oxidation potential of the light-emitting layer by 0.1 V or more is provided between the light-emitting layer and the cathode" (JP-A-2-195683). Technology. JP-A-2-195683 and JP-A-2-2-2
Although the 8-hydroxyquinoline derivative is used in the 55788 publication as the hole barrier layer based on the above concept, the luminous efficiency in the blue system is still low at 0.3 (lm · W ⁻¹ ). On the other hand, Japanese Patent Application No. 2-242669,
When the material described in Japanese Patent Application No. 2-279304 is used for the light-emitting layer, it is possible to obtain a blue-based high-luminance light emission, which will be an effective material for full-color flat panel displays and the like in the future. It can be mentioned as.
However, when these materials are used to form an element such as the anode / light-emitting layer / cathode /, anode / hole injection layer / light-emitting layer / cathode, uneven light emission or a non-light-emitting region may occur. This has been a problem for practical use of the device life, fine processing, and the like.

[0003]

Means for Solving the Problems Accordingly, the present inventors have:
As a result of intensive studies on the degree of adhesion between the light emitting layer and the cathode while maintaining the characteristics of the conventional EL element, the emission color was improved by providing a layer (adhesion layer) that improves the adhesion between the light emitting layer and the cathode. Without changing, it has been found that an EL element having improved light emission uniformity and light emission efficiency can be obtained.

The present invention has been completed based on such findings. That is, the present invention provides an anode / light-emitting layer / adhesive layer /
A cathode or an anode / a hole injection layer / a light emitting layer / an adhesive layer / a cathode are laminated in this order, and the light emitting layer has a general formula (I)

[0005]

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(Wherein R ^{1 to} R ⁴ are each a hydrogen atom,
An alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted cyclohexyl group, Or unsubstituted carbon number 6-1
8 represents an aryloxy group and an alkoxy group having 1 to 6 carbon atoms. Here, the substituent is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, and 1 to 6 carbon atoms.
An acyl group having 1 to 6 carbon atoms, a carboxyl group, a styryl group, an arylcarbonyl group having 6 to 20 carbon atoms, an aryloxycarbonyl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, Indicates a vinyl group, anilinocarbonyl group, carbamoyl group, phenyl group, nitro group, hydroxyl group or halogen. These substituents may be single or plural. R ^{1 to} R ⁴ may be the same or different from each other, and R ¹ and R ²
And R ³ and R ⁴ are bonded to a group substituting each other,
It may form a substituted or unsubstituted saturated 5-membered ring or a substituted or unsubstituted saturated 6-membered ring. Ar represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, which may be monosubstituted or plurally substituted, and the bonding site may be any of ortho, para and meta. Where A
When r is unsubstituted phenylene, R ^{1 to} R ⁴ are each an alkoxy group having 1 to 6 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, a substituted or unsubstituted naphthyl group, a biphenyl group,
It is selected from a cyclohexyl group and an aryloxy group. ), General formula (II)

[0007]

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(Wherein A and B each represent a monovalent group obtained by removing one hydrogen atom from the compound represented by the general formula (I), and may be the same or different. Q
Represents a divalent group which cuts a conjugated system. ) Or general formula (III)

[0009]

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(Where A¹Is a substituted or unsubstituted carbon
Arylene group of the formulas 6 to 20 or divalent aromatic heterocyclic group
Is shown. The bonding position may be ortho, meta or para
No. A ^TwoIs a substituted or unsubstituted ant having 6 to 20 carbon atoms
And a monovalent aromatic heterocyclic group. R^FiveAnd R
⁶Is a hydrogen atom, substituted or unsubstituted carbon number,
6-20 aryl groups, cyclohexyl groups, monovalent aromatic
Group heterocyclic group, alkyl group having 1 to 10 carbon atoms, 7 carbon atoms
-20 aralkyl groups or C1-C10 alkoxy
Represents a group. Note that R^Five, R⁶May be the same or different
No. Here, when the substituent is a single substituent,
Having a group, an aryloxy group, an amino group or a substituent
Phenyl group. R^FiveEach substituent is A
¹Is a saturated or unsaturated 5- or 6-membered ring
May be formed, and similarly, R⁶Each substituent is A^TwoAnd join
To form a saturated or unsaturated 5- or 6-membered ring
You may. Q represents a divalent group that cuts conjugation. )so
Represented and emit blue, green-blue or blue-green light
And the adhesive layer is 8-hydroxyquinoline or
It consists of a metal complex of its derivative, and its thickness is
Organic elect, characterized by being thinner than the thickness of the light emitting layer
An object of the present invention is to provide a luminescence element.

The organic EL device according to the present invention is characterized in that the anode / light-emitting layer / adhesive layer / cathode or the anode / hole injection layer / light-emitting layer / adhesive layer / cathode are laminated in this order. I do. As the anode in this EL element, a metal, an alloy, an electrically conductive compound, or a mixture thereof having a large work function (4 eV or more) as an electrode material is preferably used. Specific examples of such an electrode material include metals such as Au and dielectric transparent materials such as CuI, ITO, SnO ₂ and ZnO. The anode can be manufactured by forming a thin film from these polar substances by a method such as vapor deposition or sputtering. When light is extracted from this electrode, the transmittance is desirably higher than 10%, and the sheet resistance of the electrode is preferably several hundred Ω / □ or less. Furthermore, the film thickness depends on the material,
Usually, it is selected in the range of 10 nm to 1 μm, preferably 10 to 200 nm.

On the other hand, as the cathode, a metal, an alloy, an electrically conductive compound having a small work function (4 eV or less), and a mixture thereof as an electrode material are used. Specific examples of such an electrode material include sodium, sodium-potassium alloy, magnesium, lithium, a magnesium / copper mixture, Al / (Al ₂ O ₃ ), and indium. The cathode can be manufactured by forming a thin film of these electrode substances by a method such as vapor deposition or sputtering. The sheet resistance as an electrode is preferably several hundred Ω / □ or less, and the film thickness is usually 10
It is selected in the range of nm to 1 μm, preferably 50 to 200 nm. In this EL device, it is convenient that one of the anode and the cathode is transparent or translucent because it transmits light, so that the efficiency of extracting light is good.

Next, as the light emitting layer in the EL element, as in the case of a normal light emitting layer, an injection function (when a voltage is applied, holes can be injected from an anode or a hole injection layer, and a cathode or an electron injection layer can be used. Electrons can be injected.),
It has a transport function (it is possible to move holes and electrons by the force of an electric field) and a light-emitting function (it can provide a field for recombination of holes and electrons and emit light). It is. The thickness of this layer is not particularly limited and can be appropriately selected depending on the circumstances.
μm, particularly preferably 5 nm to 5 μm. Specific examples of the light emitting layer include the general formula (I) and the general formula (I
Compounds represented by I) or the general formula (III) are mentioned.

Here, R ^{1 to} R ⁴ in the general formula (I) are
As described above, they may be the same or different and each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (methyl group, ethyl group,
n-propyl group, i-propyl group, n-butyl group, i-
Butyl group, sec-butyl group, tert-butyl group, isopentyl group, t-pentyl group, neopentyl group, isohexyl group), alkoxy group having 1 to 6 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, etc.) , Carbon number 7-8
Aralkyl groups (benzyl group, phenethyl group, etc.) and aryl groups having 6 to 18 carbon atoms (phenyl group, biphenyl group,
A naphthyl group), a cyclohexyl group, and an aryloxy group having 6 to 18 carbon atoms (a phenoxy group, a biphenyloxy group, a naphthyloxy group, etc.).

Further, R ^{1 to} R ⁴ may have a substituent bonded thereto. That is, R ^{1 to} R ⁴ represent a substituent-containing phenyl group, a substituent-containing aralkyl group, a substituent-containing cyclohexyl group, a substituent-containing biphenyl group, and a substituent-containing naphthyl group, respectively. Here, the substituent has 1 to 1 carbon atoms.
C6 alkyl group, C1-6 alkoxy group, C7-8 aralkyl group, C6-18 aryloxy group, C1-6 acyl group, C1-6 acyloxy group , Carboxyl group, styryl group, carbon number of 6 to 2
0 arylcarbonyl group, C6-20 aryloxycarbonyl group, C1-6 alkoxycarbonyl group, vinyl group, anilinocarbonyl group, carbamoyl group, phenyl group, nitro group, hydroxyl group or halogen, A plurality may be substituted. Therefore, for example, a substituent-containing aralkyl group may be an alkyl-substituted aralkyl group (such as a methylbenzyl group or a methylphenethyl group),
Alkoxy-substituted aralkyl groups (methoxybenzyl group,
Ethoxyphenethyl group, etc.), aryloxy-substituted aralkyl group (phenoxybenzyl group, naphthyloxyphenethyl group, etc.), phenyl group-substituted aralkyl group (phenylphenethyl group, etc.) Group, dimethylphenyl group,
Ethylphenyl group, etc.), alkoxy-substituted phenyl group (methoxyphenyl group, ethoxyphenyl group, etc.) aryloxy group-substituted phenyl group (phenoxyphenyl group,
A phenyl group-substituted phenyl group (that is, a biphenylyl group). Also,
The substituent-containing cyclohexyl group includes an alkyl group-substituted cyclohexyl group (methylcyclohexyl group, dimethylcyclohexyl group, ethylcyclohexyl group, etc.), an alkoxy group-substituted cyclohexyl group (methoxycyclohexyl group,
An ethoxycyclohexyl group); an aryloxy group-substituted cyclohexyl group (phenoxycyclohexyl group, naphthyloxycyclohexyl group); and a phenyl group-substituted cyclohexyl group (phenylcyclohexyl group). The substituent-containing naphthyl group may be an alkyl-substituted naphthyl group (methylnaphthyl group, dimethylnaphthyl group, etc.), an alkoxy group-substituted naphthyl group (methoxynaphthyl group, ethoxynaphthyl group, etc.) or an aryloxy group-substituted naphthyl group (phenoxynaphthyl group, Naphthyloxynaphthyl group) and phenyl-substituted naphthyl group. As R ^{1 to} R ⁴ , among those described above, an alkyl group having 1 to 6 carbon atoms, an aryloxy group, a phenyl group, a naphthyl group, a biphenyl group, and a cyclohexyl group are preferable. These may be substituted or unsubstituted. Also, R ^{1 to} R ⁴
May be the same or different, and R ¹ and R
² and R ³ and R ⁴ may combine with each other to form a substituted or unsubstituted saturated 5-membered ring or a substituted or unsubstituted saturated 6-membered ring.

On the other hand, Ar in the general formula (I) represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and is a substituted or unsubstituted phenylene group, biphenylene group, p-
Terphenylene, naphthylene, terphenylene,
An arylene group such as a naphthalenediyl group, an anthracenediyl group, a phenanthylene diyl group, and a phenalenediyl group, which may be unsubstituted or substituted. The bonding position of methylidin (= C = CH-) may be any position such as ortho, meta, para. However, when Ar is unsubstituted phenylene, R ^{1 to} R ⁴ represent an alkoxy group having 1 to 6 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, a substituted or unsubstituted naphthyl group, a biphenyl group, a cyclohexyl group, an aryloxy group. Selected from the group. The substituent is an alkyl group (methyl group, ethyl group, n-propyl group, i-propyl group, n
-Butyl group, i-butyl group, sec-butyl group, t-butyl group, isopentyl group, t-pentyl group, neopentyl group, isohexyl group, etc.), alkoxy group (methoxy group,
Ethoxy, propoxy, i-propoxy, butyloxy, i-butyloxy, sec-butyloxy, t-butyloxy, isopentyloxy, t-
Pentyloxy group), aryloxy group (phenoxy group, naphthyloxy group, etc.), acyl group (formyl group, acetyl group, propionyl group, butyryl group, etc.), acyloxy group, aralkyl group (benzyl group, phenethyl group, etc.), phenyl Group, hydroxyl group, carboxyl group, anilinocarbonyl group, carbamoyl group, aryloxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, nitro group, halogen, which may be single or plurally substituted . The dimethylidin aromatic compound represented by the formula (I) is
The molecule has two methylidin (= C = CH-) units, and depending on the geometrical isomerism of the methylidin unit, there are four combinations, namely, cis-cis, trans-cis, cis-trans and trans-trans. There is a match. The light-emitting layer of the present invention may be any of those, or may be a mixture of geometric isomers. Particularly preferred are all trans-forms. Further, the above substituents may be bonded between the substituents to form a substituted or unsubstituted saturated 5- or 6-membered ring.

A and B in the general formula (II) each represent a monovalent group obtained by removing one hydrogen atom from the compound represented by the general formula (I), and may be the same or different. It is. Here, Q in the general formula (II) represents a divalent group that cuts a conjugated system. Here, conjugation is due to the non-polarity of π electrons, and includes conjugation double bonds or unpaired electrons or lone electron pairs. Specifically, Q is a divalent group obtained by removing one H atom from a straight-chain alkane,
For example,

[0018]

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And the like. The reason for using the divalent group that cuts the conjugated system is that A or B (namely, the compound of the general formula (I)) shown above is used alone as the organic EL device of the present invention. And the compound represented by the general formula (II) according to the present invention.
This is for keeping the EL emission color obtained when used as an L element unchanged. That is, this is for preventing the light emitting layer represented by the general formula (I) or the general formula (II) from becoming short or long. Further, it can be confirmed that the glass transition temperature (Tg) rises when a connection is made with a divalent group that cuts the conjugated system, a uniform pinhole-free microcrystalline or amorphous thin film can be obtained, and emission uniformity can be improved. Have improved. Further, by bonding with a divalent group that cuts off a conjugated system, there is an advantage that EL emission does not increase in wavelength and synthesis or purification can be easily performed.

A ¹ in the general formula (III) has 6 to 6 carbon atoms.
20 represents an arylene group, a divalent aromatic heterocyclic group, and A ² represents an aryl group having 6 to 20 carbon atoms (phenyl group, biphenyl group, naphthyl group, etc.) or a monovalent aromatic heterocyclic group.
R ⁵ and R ⁶ each represent a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a cyclohexyl group,
A monovalent aromatic heterocyclic group, an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, te
rt-butyl group, isopentyl group, t-pentyl group, neopentyl group, isohexyl group, etc., aralkyl group having 7 to 20 carbon atoms (benzyl group, phenethyl group, etc.) or 1 carbon atom
And 10 to 10 alkoxy groups (methoxy group, ethoxy group, propoxy group, butoxy group, etc.). Note that R ⁵ and R ⁶ may be the same or different. Here, in the case of single substitution, the substituent is an alkyl group, an aryloxy group, an amino group, or a phenyl group having or not having a substituent.
Each substituent of R ⁵ may be bonded to A ¹ to form a saturated or unsaturated 5- or 6-membered ring, and similarly, each substituent of R ⁶ may be bonded to A ² to form a saturated or unsaturated 5- or 6-membered ring. Alternatively, it may form an unsaturated 5- or 6-membered ring. Q represents a divalent group that cuts conjugation as described above. Further, in the present invention,
The light-emitting layer represented by the general formula (I), the general formula (II) or the general formula (III) needs to be a compound which emits blue, green-blue or blue-green light in CIE chromaticity coordinates. As a method for forming the light emitting layer, for example, a vapor deposition method,
It can be formed by thinning by a known method such as a spin coating method, a casting method, and an LB method.
In particular, a molecular deposition film is more preferable. Here, the molecular deposition film refers to a thin film formed by depositing the compound from a gaseous state or a film formed by solidifying the compound from a solution state or a liquid phase state. Can be distinguished from a thin film (molecule accumulation film) formed by the LB method by differences in the aggregated structure and higher-order structure and functional differences caused by the difference. Further, as disclosed in JP-A-59-194393, the binder is prepared by dissolving a binder such as a resin and the compound in a solvent to form a solution, and then spin-coating the solution. Can be formed into a thin film. The thickness of the light emitting layer formed in this manner is not particularly limited and can be appropriately selected depending on the situation.
m, particularly preferably in the range of 5 nm to 5 μm.

As described above, the light emitting layer of the present invention has an injection function capable of injecting holes from the anode or the hole injection layer and injecting electrons from the cathode or the electron injection transport layer when an electric field is applied. , Injected charges (electrons and holes)
It has a transport function of moving the electron by the force of an electric field, a light-emitting function of providing a field for recombination of electrons and holes, and connecting this to light emission. Note that there may be a difference between the ease of hole injection and the ease of electron injection. In addition, although the transport function represented by the mobility of holes and electrons may be large or small, it is preferable to move one of them.

Next, the hole injection layer in the present invention is not always necessary for the present device, but is preferably used for improving the light emitting performance. As the hole injection layer, materials are preferred, the mobility of holes of at least 10 ^-6 cm ² volts field of 10 ⁴ to 10 ⁶ volts / cm · to transport holes to the emitting layer at a lower electric field Seconds are even more preferred. For example, conventionally, in a photoconductive material,
Materials commonly used as charge injection / transport materials for holes and E
Any of the known materials used for the hole injection layer of the L element can be selected and used.

As the hole injection layer, for example, a triazole derivative (see US Pat. No. 3,112,197), an oxadiazole derivative (see US Pat. No. 3,189,447, etc.), an imidazole derivative (Japanese Patent Publication No. 37-16096)
And polyarylalkane derivatives (U.S. Pat. Nos. 3,615,402, 3,820,989, 3, and 3).
542,544, JP-B No. 45-555, 51
-10983, JP-A-51-93224,
Nos. 55-17105 and 56-4148,
JP-A-55-108667, JP-A-55-156953, JP-A-56-36656, etc.), pyrazoline derivatives and pyrazolone derivatives (U.S. Pat. Nos. 3,180,729 and 4,278,746; JP-A-55-8806).
No. 4, No. 55-88065, No. 49-105
Nos. 537, 55-51086, 56-8
Nos. 0051 and 56-88141 and 57-88.
Nos. 45545, 54-112637 and 5
5-74546, etc.), phenylenediamine derivatives (U.S. Pat. No. 3,615,404, JP-B-51-1)
No. 0105, No. 46-3712, No. 47-2
5336, JP-A-54-53435, and 5
Nos. 4-110536 and 54-119925, and arylamine derivatives (US Pat. No. 3,567,45).
No. 0, No. 3,180,703, No. 3,240,597, No. 3,658,520, No. 4,232,103,
Nos. 4,175,961 and 4,012,376, JP-B-49-35702, JP-A-39-27577,
JP-A-55-144250, JP-A-56-11913
No. 2, No. 56-22437, West German Patent No. 1,11
No. 0,518, etc.), amino-substituted chalcone derivatives (see U.S. Pat. No. 3,526,501, etc.), oxazole derivatives (described in U.S. Pat. 4
6234), fluorenone derivatives (see JP-A-54-110837, etc.) and hydrazone derivatives (US Pat. No. 3,717,462, JP-A-54-591).
No. 43, No. 55-52063, No. 55-52
Nos. 064 and 55-46760 and 55-8
Nos. 5495, 57-11350, 57-
148,749, JP-A-2-311591, etc.), stilbene derivatives (JP-A-61-210363)
Gazette, JP-A-61-228451, JP-A-61-146
No. 42, No. 61-72255, No. 62-47
Nos. 646 and 62-36674 and 62-1
Nos. 0652, 62-30255, 60-
Nos. 93445, 60-94462, 60
1747474 and 60-175052). Further, as a hole injection transport material, a silazane derivative (US Pat.
950), polysilanes (JP-A-2-2049)
No. 96), an aniline-based copolymer (JP-A-2-282)
No. 263), and a conductive polymer oligomer, particularly a thiophene oligomer, described in Japanese Patent Application No. 1-211399.

In the present invention, these compounds can be used as a hole injecting layer. The following porphyrin compounds (those described in JP-A-63-2955695) and aromatic tertiary compounds Amine compounds and styrylamine compounds (U.S. Pat. No. 4,127,412, JP-A-53-27033, JP-A-54-58445, JP-A-54-149634, and JP-A-54-64299).
Gazette, JP-A-55-79450, JP-A-55-1442
No. 50, No. 56-119132, No. 61-2
No. 95558, No. 61-98353, No. 63
It is particularly preferable to use the aromatic tertiary amine compound.

Representative examples of the porphyrin compound include:
Porphine, 1,10,15,20-tetraphenyl-
21H, 23H-porphine copper (II), 1,10,1
5,20-tetraphenyl 21H, 23H-porphine cuprous (II), 5,10,15,20-tetrakis (pentafluorophenyl) -21H, 23H-porphine,
Silicon phthalocyanine oxide, aluminum phthalocyanine chloride, phthalocyanine (metal-free), dilithium phthalocyanine, copper tetramethyl phthalocyanine,
Examples thereof include copper phthalocyanine, chromium phthalocyanine, zinc phthalocyanine, lead phthalocyanine, titanium phthalocyanine oxide, magnesium phthalocyanine, and copper octamethyl phthalocyanine. Representative examples of the aromatic tertiary amine compound and styrylamine compound include N, N, N ', N'-tetraphenyl-4,
4'-diaminophenyl, N, N'-diphenyl-N,
N'-di (3-methylphenyl) -4,4'-diaminobiphenyl (TPDA), 2,2-bis (4-di-p-
Tolylaminophenyl) propane, 1,1-bis (4-
Di-p-tolylaminophenyl) cyclohexane, N,
N, N ', N'-tetra-p-tolyl-4,4'-diaminobiphenyl, 1,1-bis (4-di-p-tolylaminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino -2-methylphenyl) phenylmethane, bis (4-di-p-tolylaminophenyl) phenylmethane, N, N'-diphenyl-N, N'-di (4-methoxyphenyl) -4,4'-diamino Biphenyl, N, N, N ', N'-tetraphenyl-4,4'
-Diaminodiphenyl ether, 4,4'-bis (diphenylamino) quadriphenyl, N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino)
-4 '-[4 (di-p-tolylamino) styryl] stilbene, 4-N, N-diphenylamino- (2-diphenylvinyl) benzene, 3-methoxy-4'-N, N-
Examples include diphenylaminostilbenzene, N-phenylcarbazole, and aromatic dimethylidin compounds.

The hole injection layer in the EL device of the present invention comprises:
The compound can be formed by forming a film by a known thinning method such as a vacuum evaporation method, a spin coating method, a casting method, and an LB method. The thickness of this hole injection layer is
Although there is no particular limitation, it is usually 5 nm to 5 μm. The hole injection layer may be composed of one or two or more of these hole injection transport materials, or a hole injection layer composed of a compound different from the hole injection layer. May be done. Organic EL obtained by the present invention
As a device configuration of the device, it is preferable to use a material having high adhesion to the light emitting layer and the cathode as a layer (adhesion layer) for improving the adhesion between the newly added light emitting layer and the cathode. As a material for such an adhesive layer, a metal complex of 8-hydroxyquinoline or a derivative thereof can be given. Specifically, it is a metal chelate oxinoid compound containing a chelate of oxine (generally 8-quinolinol or 8-hydroxyquinoline). Such compounds exhibit a high level of performance and are easily formed into thin film form. Examples of the oxinoid compound satisfy the following structural formula.

[0027]

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(Wherein, Mt represents a metal, n is an integer of 1 to 3, and Z is independently at each position, and is used to complete at least two or more fused aromatic rings. Here, the necessary atoms are shown.) Here, the metal represented by Mt is a metal that can be a monovalent, divalent or trivalent metal, for example, an alkali metal such as lithium, sodium or potassium, magnesium or It is an alkaline earth metal such as calcium, or an earth metal such as boron or aluminum. Any of the monovalent, divalent or trivalent metals generally known to be useful chelate compounds can be used.

Z represents an atom in which at least one of two or more fused aromatic rings forms a heterocyclic ring composed of azole or azine. Here, if necessary, another different ring can be added to the fused aromatic ring. To avoid adding bulky molecules without functional improvement, the number of atoms represented by Z is 18
It is preferable to maintain the following. Further, specific examples of chelated oxinoid compounds include tris (8-
(Quinolinol) aluminum, bis (8-quinolinol) magnesium, bis (benzo-8-quinolinol)
Zinc, bis (2-methyl-8-quinolinol) aluminum oxide, tris (8-quinolinol) indium, tris (5-methyl-8-quinolinol) aluminum, lithium 8-quinolinol, tris (5-chloro-8-quinolinol) Gallium, bis (5-chloro-8
-Quinolinol) calcium, 5,7-dichloro-8-
Quinolinol aluminum, tris (5,7-dibromo-8-hydroxyquinolinol) aluminum and the like. Further, the thickness of the adhesive layer needs to be smaller than the thickness of the light emitting layer, and is preferably 1 to 50 nm, particularly preferably 5 to 30 nm. The reason for limiting the film thickness in this way is to maintain the emission color in a blue color.

The method for forming the adhesive layer includes, for example, a spin coating method, a casting method, and a vapor deposition method. Preferably, like the light emitting layer and the hole injection layer, a vapor deposition method is preferable.
Here, examples of compounds used for the light emitting layer are shown below.

[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

Next, the present invention will be described in more detail by reference examples, examples and comparative examples. Reference Example 1 [Production method of 4,4'-bis (2,2'-diphenylvinyl) biphenyl] Production of arylene group-containing phosphorus compound 9.0 g of 4,4'-bis (bromomethyl) biphenyl and 11 g of triethyl phosphite were prepared. The mixture was heated and stirred at 140 ° C. for 6 hours in an oil bath under a stream of argon. afterwards,
Excess triethyl phosphite and by-produced ethyl bromide were distilled off under reduced pressure. After standing overnight, 9.5 g of white crystals (yield 80
%). The analysis results of this are as follows. Melting point: 97.0-100.0 ° C. Measurement by proton nuclear magnetic resonance [ ¹ H-NMR (CDCl ₃ )]: δ = 7.3 to 8.4 ppm (m; 8H, biphenylene ring-H) δ = 4. 1ppm (d; 4H, J = 20Hz (31 P- 1 H _{coupling) P-CH 2 δ = 3.7ppm} (q; 8H, methylene ethoxy _{-CH 2) δ = 1.0ppm (t} ; 12H, ethoxy Group methyl-CH ₃ ) From the above results, the above product is represented by the following formula

[0042]

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It was confirmed that the compound was an arylene group-containing phosphorus compound (phosphonate: Mw = 454.5).

Production of Aromatic Dimethylidin Compound 4.5 g of the phosphonate and 5.5 g of benzophenone obtained in Reference Example 1 were dissolved in 100 ml of dimethyl sulfoxide, and potassium-t-butoxide 2.2 was added thereto.
g, and the mixture was stirred at room temperature for 4 hours under a stream of argon.
Left overnight. 100 ml of methanol was added to the obtained mixture, and the precipitated crystals were filtered. The filtered product is washed three times with 100 ml of water, followed by methanol 10
The column was sufficiently washed three times with 0 ml and subjected to column purification to obtain 2.0 g of a yellow-orange powder (yield 26%). The analysis results of this are as follows. Melting point: 204.5-206.5 ° C. Measurement by ¹ H-NMR (CDCl ₃ ): δ = 6.7-7.3 ppm (m; 30H, terminal phenyl ring—
H, central biphenylene and methylidin = C = CH
-) Elemental analysis: as follows as the composition formula C ₄₀ H _30.
The values in parentheses are theoretical values. C: 94.23% (94.08%) H: 5.84% (5.92%) N: 0.000% (0%) Infrared (IR) absorption spectrum (KBr tablet method)
Is as follows. ν _{C = C} 1520, 1620 cm ^{−1 Further} , the molecular ion peak m of the target substance from the mass spectrum
/ Z = 510 was detected. From the above, the above product, a pale yellow powder, has the following formula

[0045]

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4,4'-bis (2,2'-
Diphenylvinyl) biphenyl.

REFERENCE EXAMPLE 2 [Production method of 4,4'-bis (2,2'-di (4-t-butylphenyl) vinyl) biphenyl] Production of arylene group-containing phosphorus compound Same as Reference Example 1. Production of Aromatic Dimethylidin Compound 1.8 g of the phosphonate obtained in Reference Example 2 and 4,
2.4 g of 4'-di-t-butylbenzophenone was dissolved in 100 ml of dimethyl sulfoxide, and 1.0 g of potassium-t-butoxide was added thereto. The mixture was stirred at room temperature for 4 hours under a stream of argon and left overnight. did. 100 ml of methanol was added to the obtained mixture, and the precipitated crystals were filtered. The filtered product was sufficiently washed three times with 100 ml of water and then three times with 100 ml of methanol and subjected to column purification to obtain 1.0 g of a pale yellow powder (yield: 35%). The analysis results of this are as follows. Melting point: 293.0-296.0 ° C. ¹ H-NMR (CDCl ₃ ) δ = 7.0-7.4 ppm (m; 24H, terminal phenyl ring—
H, central biphenylene-H) δ = 6.9 ppm (s; 2H, methylidin = C =
CH-) δ = 1.3 ppm (s; 36H, t-butyl group -C
(CH ₃ ) ₃ ) Elemental analysis value: The following is the composition formula C ₅₆ H ₆₂ . The values in parentheses are theoretical values. C: 91.42% (91.50%) H: 8.45% (8.50%) N: 0.000% (0%) Infrared (IR) absorption spectrum (KBr tablet method)
Is as follows. ν _{C = C} 1520, 1610 cm ^{−1 Further} , the molecular ion peak m
/ Z = 734 was detected. From the above, the above product, a pale yellow powder, has the following formula

[0048]

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4,4'-bis (2,2'-
It was confirmed to be di (4-t-butylphenyl) vinyl) biphenyl.

Reference Example 3 [4,4'-bis (2- (4-t-butylphenyl)-
Production method of 2-phenylvinyl) biphenyl] Production of arylene group-containing phosphorus compound Same as Reference Example 1. Production of aromatic dimethylidin compound 3.0 g of the phosphonate obtained in Reference Example 3 and 4-t
4.1 g of -butylbenzophenone was dissolved in 100 ml of dimethyl sulfoxide, and potassium-t-
1.5 g of butoxide was added, and the mixture was stirred at room temperature for 4 hours under a stream of argon, and then left overnight. 100 ml of methanol was added to the obtained mixture, and the precipitated crystals were filtered. The filtered product was sufficiently washed three times with 100 ml of water and then three times with 100 ml of methanol and subjected to column purification to obtain 1.8 g of a pale yellow powder (yield: 38).
%). The analysis results of this are as follows. Melting point: 202.0-204.0 ° C. ¹ H-NMR (CDCl ₃ ) δ = 7.0-7.4 ppm (m; 26H, terminal phenyl ring—
H, central biphenylene-H) δ = 6.9 ppm (s; 2H, methylidin = C =
CH-) δ = 1.3 ppm (s; 18H, t-butyl group -C
(CH ₃ ) ₃ ) Elemental analysis value: The following is the composition formula C ₄₈ H ₄₆ . The values in parentheses are theoretical values. C: 92.38% (92.56%) H: 7.18% (7.44%) N: 0.000% (0%) Infrared (IR) absorption spectrum (KBr tablet method)
Is as follows. ν _{C = C} 1520, 1610 cm ^{−1 Further} , the molecular ion peak m
/ Z = 622 was detected. From the above, the yellow-orange powder, which is the product, has the following formula

[0051]

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4,4'-bis (2- (4-
It was confirmed to be t-butylphenyl) -2-phenylvinyl) biphenyl.

REFERENCE EXAMPLE 4 (Production method of 4,4'-bis (2,2'-di-p-tolylvinyl) biphenyl) Production of arylene group-containing phosphorus compound Same as Reference Example 1. Production of Aromatic Dimethylidin Compound 4.0 g of the phosphonate obtained in Reference Example 4 and 4,
5.0 g of 4'-dimethylbenzophenone was dissolved in 60 ml of tetrahydrofuran, 2.0 g of potassium tert-butoxide was added, and the mixture was refluxed and stirred under an argon stream, and left overnight. After the solvent of the obtained mixture was distilled off, 200 ml of methanol was added, and the precipitated crystals were filtered. The filtered product is then washed 3 times with 100 ml of water, followed by 3 times with 100 ml of methanol.
After sufficiently washing twice and recrystallizing with benzene, 1.0 g of a pale yellow powder was obtained (yield: 22%). Its melting point was 153-155 ° C. The ¹ H-
The NMR analysis results are as follows. ¹ H-NMR (CDCl ₃ ) δ = 6.3 to 7.3 ppm (m; 26H, aromatic ring —H and methylidin CH ＝ C—) δ = 1.0 to 2.0 ppm (s; 12H, p-tolylmethyl) group -CH ₃₎ further the elemental analysis results are as follows as the composition formula C ₄₄ H _38. The values in parentheses are theoretical values. C: 93.10% (93.24%) H: 7.04% (6.76%) N: 0.000% (0%) Infrared (IR) absorption spectrum (KBr tablet method)
Is as follows. ν _{C = C} 1520, 1610 cm ^{−1 Further} , the molecular ion peak m / Z = 566 of the target substance was detected from the mass spectrum. From the above, the above product, a pale yellow powder, has the following formula

[0054]

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4,4'-bis (2,2'-
Di-p-tolylvinyl) biphenyl.

Reference Example 5 [Production method of 4,4'-bis (2,2'-di-p-methoxyphenylvinyl) biphenyl] Production of arylene group-containing phosphorus compound Same as Reference Example 1. Production of Aromatic Dimethylidin Compound 3.0 g of the phosphonate obtained in Reference Example 5 and 4,
4.8 g of 4'-di-methoxybenzophenone was dissolved in 100 ml of dimethyl sulfoxide, and 1.5 g of potassium-t-butoxide was added thereto.
After stirring at room temperature for 4 hours, the mixture was left overnight. 100 ml of methanol was added to the obtained mixture, and the precipitated crystals were filtered. Filter the product with 100 ml of water 3
This was followed by thorough washing with methanol (100 ml) three times and column purification to obtain 1.1 g of a yellow-green powder (yield: 26%). The analysis results of this are as follows. Melting point: 218 to 218.5 ° C ¹ H-NMR (CDCl ₃ ) δ = 6.7 to 7.3 ppm (m; 26H, terminal phenyl ring-
H, central biphenylene-H, methylidin = C = CH
−) Δ = 3.8 ppm (s; 12H, terminal methoxy-OC)
H ₃ ) Elemental analysis value: The following is the composition formula C ₄₄ H ₃₈ O ₄ . The values in parentheses are theoretical values. C: 83.51% (83.78%) H: 5.89% (6.07%) N: 0.000% (0%) Infrared (IR) absorption spectrum (KBr tablet method)
Is as follows. ν _{C = C} 1520, 1620 cm ^{−1 Further} , the molecular ion peak m of the target substance from the mass spectrum
/ Z = 630 was detected. From the above, the yellow-green powder, which is the product, has the following formula

[0057]

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4,4'-bis (2,2'-
Di-p-methoxyphenylvinyl) biphenyl.

Reference Example 6 [Production of 3,3'-dimethyl-4,4'-bis (2,2'-diphenylvinyl) biphenyl] Production of arylene group-containing phosphorus compound 3,3'-dimethyl-4,4 '-Bis (bromomethyl)
12 g of biphenyl and 12 g of triethyl phosphite were heated and stirred at 130 ° C. for 6 hours in an oil bath under a stream of argon. Thereafter, excess triethyl phosphite and by-produced ethyl bromide were distilled off under reduced pressure. After standing overnight, the obtained white crystals were recrystallized from benzene-hexane to obtain 15.2 g (yield: 97%) of white crystals. The analysis results of this are as follows. Melting point: 90.5-91.5 ° C. ¹ H-NMR (CDCl ₃ ) δ = 7.2 ppm (s; 6H, biphenyl ring-H) δ = 3.1 ppm (d; 4H, J = 20 Hz ( ³¹ P− ¹ H coupling) P-CH ₂ ) δ = 4.0 ppm (q; 8H, ethoxy group methylene-C
H ₂ ) δ = 1.2 ppm (t; 12H, ethoxy group methyl-C
H ₃ ) δ = 2.5 ppm (s; 6H, methyl-CH of biphenyl ring)
₃ ) From the above results, it was confirmed that the above product was an arylene group-containing phosphorus compound (phosphonate) represented by the following formula.

[0060]

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Production of Aromatic Dimethylidin Compound 0.75 g of the phosphonate and 0.6 g of benzophenone obtained in the above Reference Example 6 were dissolved in 100 ml of dimethyl sulfoxide, and the solution was dissolved in 0.1 ml of potassium tert-butoxide.
35 g was added, and the mixture was stirred at room temperature for 4 hours under an argon stream, and then left overnight. The resulting mixture is mixed with methanol 100
Milliliter was added and the precipitated crystals were filtered. The filtered product was sufficiently washed three times with 100 ml of water and then three times with 100 ml of methanol and subjected to column purification to obtain 0.45 g of a pale yellow powder (yield 54%). The analysis results of this are as follows. Melting point: 201.8-202.8 ° C. ¹ H-NMR (CDCl ₃ ) δ = 6.9-7.3 ppm (m; 26H, terminal phenyl ring—
H, central biphenylene-H) δ = 6.8 ppm (s; 2H, methylidin = C =
CH-) δ = 2.2 ppm (s; 6H, central biphenylene-C
H ₃ ) Elemental analysis value: The following is the composition formula C ₄₂ H ₃₄ . The values in parentheses are theoretical values. C: 93.54% (93.64%) H: 6.22% (6.36%) N: 0.000% (0%) Infrared (IR) absorption spectrum (KBr tablet method)
Is as follows. ν _{C = C} 1520, 1610 cm ^{−1 Further} , the molecular ion peak m
/ Z = 538 was detected. From the above, the above product, a pale yellow powder, has the following formula

[0062]

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3,3'-dimethyl-4,
It was confirmed to be 4'-bis (2,2'-diphenylvinyl) biphenyl.

Reference Example 7

[0065]

Embedded image

[0066]

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O, O-Diethyldiphenylmethylphosphonate (11.2 g, 0.037 mol) and 4-methyl-4'-
In a stream of argon gas, 7.2 g (0.036 mol) of formylbiphenyl was dissolved in 200 ml of anhydrous dimethyl sulfoxide, and 4.1 g of potassium tert-butoxide (0.1 g) was dissolved.
036 mol) was added. Then, after stirring at room temperature for 6 hours, 200 ml of methanol was added to obtain 8.0 g (yield: 64%) of precipitated white powder. This compound had a melting point of 128.0-129.0 ° C. Of the product ¹ H-
NMR is as follows. ¹ H-NMR (CDCl ₃ ) δ = 6.8-7.4 ppm (m; 19H, aromatic ring —H and methylidin —CH ＝ C ＝) δ = 2.3 ppm (s; 3H, methyl group —CH ₃ )

[0068]

[0069]

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6.5 g of the compound obtained in the above Reference Example 7 (
0.018 mol) and 3.5 g of N-bromosuccinimide (0.1 g).
019 mol) and 0.7 g of benzoyl peroxide in carbon tetrachloride
The suspension was suspended in 50 ml and stirred vigorously at an external temperature of 100 ° C. After refluxing and stirring for 4 hours, the solvent was distilled off.
10 g of a pale yellow powder was obtained. This was purified by a silica gel column (solvent: methylene chloride) to obtain 5.3 g (yield 70%) of white powder. The melting point of this compound is 127.0-128.
It was 0 ° C. The ¹ H-NMR of the product is as follows. ¹ H-NMR (CDCl ₃ ) δ = 7.6-6.9 ppm (m; 19H, aromatic ring-H and methylidin-CH = C =) δ = 4.5 ppm (s; 2H, bromomethyl-CH ₂ Br)

[0071]

[0072]

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The compound obtained in Reference Example 7 (5.3 g,
0.0125 mol) to 13.0 g (0.03) of triethyl phosphite.
79 mol), and the mixture was heated and stirred at 110 ° C. for 6 hours under an argon gas atmosphere. After standing overnight, excess triethyl phosphite was distilled off under reduced pressure to obtain a yellow paste-like compound. This was purified by a silica gel column (solvent: methylene chloride was used first, then methylene chloride: acetone was changed to 1: 1 (volume ratio)) to obtain 6.0 g (quantitative) of a pale yellow powder. The melting point of this compound was 62 to 64 ° C. The ¹ H-NMR of the compound is as follows. ¹ H-NMR (CDCl ₃ ) δ = 7.0-7.4 ppm (m; 18H, aromatic ring-H) δ = 6.9 ppm (s; 1H, methylidin-CH = C =
) Δ = 4.0 ppm (q; 4H, ethoxy group -CH _2- ) δ = 3.1 ppm (d; 2H, -CH ₂ -P J = 16 Hz) δ = 1.3 ppm (t; 6H, ethoxy group-) CH ₃ )

The phosphonate obtained in Reference Example 5 above.
8 g (0.0093 mol) were suspended in 150 ml of dimethyl sulfoxide under a stream of argon gas, and 2.0 g of the compound (diketone) obtained in Reference Example 7 was added thereto.
0.0049 mol) and 1.2 g of potassium tert-butoxide (
0.010 mol). The solution presents a red-brown suspension,
Stirred at room temperature for 6 hours. After leaving overnight, the solvent was distilled off, 700 ml of methanol was added to the reaction mixture, and the precipitated pale yellow powder was collected by filtration. This was purified with a silica gel column (solvent: CH ₂ Cl ₂ , diameter 40 mm × length 230 mm) to obtain 0.9 (yield 20%) amorphous crystals. Its Tg was 91.7 ° C. according to DSC measurement. The melting point of this compound was 203.0 to 204.0 ° C. The ¹ H-NMR of the product was as follows. ¹ H-NMR (CDCl ₃ ) δ = 6.8 to 7.9 ppm (m; 56H, aromatic ring and methylidin-CHＣC）) δ = 2.5 ppm (s, 6H, methyl group —CH ₃ ) From the mass spectrum (MS), only the molecular ion peak m / Z = 1062 of the target substance was detected. Furthermore,
The results of elemental analysis are as follows, with C ₈₂ H ₆₂ O as the composition formula. The values in parentheses are theoretical values. C: 92.31% (92.62%) H: 5.41% (5.88%) N: 0.000% (0%) Infrared (IR) absorption spectrum (KBr tablet method)
Is as follows. ν _{C = C} 1520, 1610 cm ⁻¹ or more, the above compound has the following formula

[0075]

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It was confirmed that the compound was represented by the following formula:

Example 1 ITO was placed on a 25 mm × 75 mm × 1.1 mm glass substrate.
Was formed to a thickness of 100 nm by vapor deposition.
It was a holding substrate. Put this substrate in isopropyl alcohol
Ultrasonic cleaning in pure water for 5 minutes.
Next, UV ozone cleaning was performed by Samco Internashi Co., Ltd.
The measurement was performed for 10 minutes using a device manufactured by National Research Laboratory. This transparent support
The substrate is mounted on a commercially available evaporation system (Nihon Vacuum Technology Co., Ltd.).
Fixed to a plate holder and used as a molybdenum resistance heating boat
N, N'-bis (3-methylphenyl) -N, N'-di
Phenyl [1,1'-biphenyl] -4,4'-diami
(TPD) 200mg, different molybdenum
Add 4,4'-bis (2,2'-diphenylvinyl
Le) biphenyl (DPVBi, ionization energy:
5.9 eV) and put the vacuum chamber into 1 × 10^-FourP
The pressure was reduced to a. After that, the boat with TPD was
Heat to 5 to 220 ° C. and deposit TPD at a deposition rate of 0.1 to 0.3.
deposited on a transparent support substrate at a thickness of 60 nm / s.
A hole injection layer was formed. The substrate temperature at this time is room temperature.
Was. Without removing this from the vacuum chamber, the hole injection layer
On top of the above, DPVBi is used as a light emitting layer from another boat
40 nm. The evaporation conditions were boat temperature of 24.
At 0 ° C, deposition rate is 0.1 to 0.3 nm / s, substrate temperature is room temperature
Met. Take this out of the vacuum chamber and place it on the light emitting layer
Install a stainless steel mask,
And fixed it to Next, tris (8
-Quinolinol) aluminum (Alq_Three, Ionization
Energy: 5.6eV) 200mg
did. In addition, the molybdenum resistance heating boat
1g of shim ribbon and another tungsten bath
500 mg of silver wire was put in the ket and evaporated. That
After that, the vacuum chamber is ^-FourAfter reducing the pressure to Pa
_ThreeIs heated to 230 ° C and Alq_ThreeTo 0.
20 nm was deposited at a deposition rate of 01 to 0.03 nm / s.
In addition, silver is simultaneously resistance heated at a deposition rate of 0.1 nm / s.
Magnesium from the other molybdenum boat
And began to deposit at a deposition rate of 1.4 nm / s. Above conditions
A magnesium and silver mixed metal electrode on the light emitting layer
0 nm was laminated and deposited to form a counter electrode.

Example 2 ITO was placed on a glass substrate of 25 mm × 75 mm × 1.1 mm.
Was formed to a thickness of 100 nm by a vapor deposition method to obtain a transparent support substrate. This substrate was subjected to ultrasonic cleaning for 5 minutes in isopropyl alcohol and further for 5 minutes in pure water, and then to UV ozone cleaning for 10 minutes using an apparatus manufactured by Samco International Laboratories. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Nippon Vacuum Technology Co., Ltd.), and N, N was attached to a molybdenum resistance heating boat.
Put 200 mg of N'-bis (3-methylphenyl) -N, N'-diphenyl [1,1'-biphenyl] -4,4'-diamine (TPD), and add 4,4'- 200 mg of bis (4-t-butylphenylvinyl) biphenyl (DTBPVBi, ionization energy: 5.9 eV) was charged, and the vacuum chamber was set to 1 × 10 ^−4.
The pressure was reduced to Pa. After that, two boats with TPD
Heat to 15-220 ° C. and deposit TPD at a deposition rate of 0.1-0.1.
Deposited on a transparent support substrate at 3 nm / s, and a film thickness of 60 nm
Was formed into a hole injection layer. The substrate temperature at this time was room temperature. Without taking this out from the vacuum chamber, DTBPVBi was deposited as a light emitting layer to a thickness of 40 nm from another boat on the hole injection layer. The deposition conditions were a boat temperature of 330 ° C., a deposition rate of 0.1 to 0.3 nm / s, and a substrate temperature of room temperature. This was taken out of the vacuum chamber, a stainless steel mask was placed on the light emitting layer, and fixed again to the substrate holder. Next, tris (8-quinolinol) aluminum (Alq ₃ ) was added to the molybdenum boat.
00 mg was put in a vacuum chamber. Furthermore, put 1g of magnesium ribbon into molybdenum resistance heating boat,
Also put 50 silver wires in a different tungsten basket
0 mg was deposited. Thereafter, the vacuum chamber is set to 1 × 10 ⁻⁴ Pa
After decompression, the boat containing Alq ₃ was cooled to 230 ° C.
Then, Alq ₃ was deposited at a deposition rate of 0.01 to 0.03 nm / s to a thickness of 20 nm. Further, silver was simultaneously deposited at a deposition rate of 0.1 nm / s by a resistance heating method and magnesium was deposited from the other molybdenum boat at a deposition rate of 1.4 nm / s. Under the above conditions, a mixed metal electrode of magnesium and silver was deposited to a thickness of 150 nm on the light emitting layer to form a counter electrode.

Example 3 ITO was placed on a 25 mm × 75 mm × 1.1 mm glass substrate.
Was formed to a thickness of 100 nm by vapor deposition.
It was a holding substrate. Put this substrate in isopropyl alcohol
Ultrasonic cleaning for 5 minutes in pure water for 5 minutes
Next, UV ozone cleaning was performed by Samco International
This was performed for 10 minutes using a device manufactured by Le Labs. This transparent support group
The plate was placed on a substrate evaporator (available from Nihon Vacuum Technology Co., Ltd.)
To the molybdenum resistance heating boat.
N'-bis (3-methylphenyl) -N, N'-dife
Nyl [1,1'-biphenyl] -4,4'-diamine
(TPD) 200mg, another molybdenum bo
4,4'-bis [2- (4-t-butylphenyl)
L) -2-biphenylvinyl] biphenyl (TBPVB
i, ionization energy: 5.85 eV) 200 mg
1 × 10 vacuum chamber^-FourThe pressure was reduced to Pa. Then TP
The boat containing D is heated to 215 to 220 ° C.
PD is deposited on a transparent support substrate at a deposition rate of 0.1 to 0.3 nm / s.
A hole injection layer having a thickness of 60 nm was formed by vapor deposition. This
The substrate temperature at this time was room temperature. Take this from the vacuum chamber
Another boat on top of the hole injection layer
A 40 nm layer of TBPVBi was deposited as a light emitting layer.
The deposition conditions are as follows: boat temperature is 280 ° C and deposition rate is 0.1 to 0.1.
3 nm / s and the substrate temperature was room temperature. This is from the vacuum chamber
Take out and place a stainless steel
The disk was set and fixed to the substrate holder again. Next
Tris (8-quinolinol) aluminum on a boat made of buden
Um (Alq_Three) Into a vacuum chamber
Was. In addition, the resistance heating boat made of molybdenum
Um ribbon 1g, another tungsten basket
500 mg of a silver wire was put into the container and evaporated. afterwards,
1 × 10 vacuum chamber^-FourAfter reducing the pressure to Pa_Threeof
Heat the boat into 230 ° C _ThreeTo 0.01
20 nm was deposited at a deposition rate of 0.03 nm / s. Further
At the same time, silver was deposited at a deposition rate of 0.1 nm / s by resistance heating.
More magnesium from the other molybdenum boat
Deposition was started at a deposition rate of 1.4 nm / s. Under the above conditions,
A mixed metal electrode of gnesium and silver is placed on the light emitting layer for 150n.
m layers were deposited to form a counter electrode.

Example 4 ITO was placed on a 25 mm × 75 mm × 1.1 mm glass substrate.
Was formed to a thickness of 100 nm by a vapor deposition method to obtain a transparent support substrate. This substrate was subjected to ultrasonic cleaning for 5 minutes in isopropyl alcohol and further for 5 minutes in pure water, and then to UV ozone cleaning for 10 minutes using an apparatus manufactured by Samco International Laboratories. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Nippon Vacuum Technology Co., Ltd.), and N, N was attached to a molybdenum resistance heating boat.
Put 200 mg of N'-bis (3-methylphenyl) -N, N'-diphenyl [1,1'-biphenyl] -4,4'-diamine (TPD), and add 4,4'- Bis (2,2-di-p-trivinyl)
Biphenyl (DTVBi, ionization energy: 5.85
eV), and the pressure in the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa. After that, the boat containing TPD was 215-2
Heat to 20 ° C. to deposit TPD at a deposition rate of 0.1 to 0.3 nm /
In step s, a hole injection layer having a thickness of 60 nm was formed by vapor deposition on the transparent support substrate. The substrate temperature at this time was room temperature.
Without taking this out of the vacuum chamber, DTVBi was used as a light emitting layer from another boat on the hole injection layer.
0 nm layer deposition was performed. The evaporation conditions are as follows: boat temperature is 275 ° C.
, The deposition rate was 0.1 to 0.3 nm / s, and the substrate temperature was room temperature. This was taken out of the vacuum chamber, a stainless steel mask was placed on the light emitting layer, and fixed again to the substrate holder. Next, 200 mg of tris (8-quinolinol) aluminum (Alq ₃ ) was put into a molybdenum boat, and the boat was attached to a vacuum chamber. Further, 1 g of a magnesium ribbon was placed in a molybdenum resistance heating boat, and 500 mg of silver wire was deposited in a different tungsten basket and vapor-deposited. Thereafter, the pressure in the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa, and then the boat containing Alq ₃ was heated to 230 ° C., and Alq ₃ was evaporated at a deposition rate of 0.01 to 0.03 nm / s.
0 nm was deposited. Further, silver was simultaneously deposited at a deposition rate of 0.1 nm / s by a resistance heating method and magnesium was deposited from the other molybdenum boat at a deposition rate of 1.4 nm / s. Under the above conditions, a mixed metal electrode of magnesium and silver was deposited to a thickness of 150 nm on the light emitting layer to form a counter electrode.

Example 5 ITO was placed on a 25 mm × 75 mm × 1.1 mm glass substrate.
Was formed to a thickness of 100 nm by a vapor deposition method to obtain a transparent support substrate. This substrate was subjected to ultrasonic cleaning for 5 minutes in isopropyl alcohol and further for 5 minutes in pure water, and then to UV ozone cleaning for 10 minutes using an apparatus manufactured by Samco International Laboratories. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Nippon Vacuum Technology Co., Ltd.), and N, N was attached to a molybdenum resistance heating boat.
Put 200 mg of N'-bis (3-methylphenyl) -N, N'-diphenyl [1,1'-biphenyl] -4,4'-diamine (TPD) and add 4,4'-diamine to another molybdenum boat. 200 mg of bis (2,2-di-p-methoxyphenylvinyl) biphenyl (DMVBi, ionization energy: 5.85 eV) was charged, and the vacuum chamber was 1 × 1.
The pressure was reduced to 0 ^-4 Pa. Thereafter, the boat containing TPD is heated to 215 to 220 ° C., and TPD is deposited at a deposition rate of 0.1.
Deposited on a transparent support substrate at a thickness of about 0.3 nm / s to a film thickness of 60
A hole injection layer having a thickness of nm was formed. The substrate temperature at this time was room temperature. Without taking it out of the vacuum chamber, 40 nm of DMVBi was deposited and deposited as a light emitting layer from another boat on the hole injection layer. The deposition conditions were a boat temperature of 320 ° C., a deposition rate of 0.1 to 0.3 nm / s, and a substrate temperature of room temperature. This was taken out of the vacuum chamber, a stainless steel mask was placed on the light emitting layer, and fixed again to the substrate holder. Next, tris (8-quinolinol) aluminum (Alq ₃ ) was added to the molybdenum boat.
00 mg was put in a vacuum chamber. Furthermore, put 1g of magnesium ribbon into molybdenum resistance heating boat,
Also put 50 silver wires in a different tungsten basket
0 mg was deposited. Thereafter, the vacuum chamber is set to 1 × 10 ⁻⁴ Pa
After decompression, the boat containing Alq ₃ was cooled to 230 ° C.
Then, Alq ₃ was deposited at a deposition rate of 0.01 to 0.03 nm / s to a thickness of 20 nm. Further, silver was simultaneously deposited at a deposition rate of 0.1 nm / s by a resistance heating method and magnesium was deposited from the other molybdenum boat at a deposition rate of 1.4 nm / s. Under the above conditions, a mixed metal electrode of magnesium and silver was deposited to a thickness of 150 nm on the light emitting layer to form a counter electrode.

Example 6 ITO was placed on a glass substrate of 25 mm × 75 mm × 1.1 mm.
Was formed to a thickness of 100 nm by a vapor deposition method to obtain a transparent support substrate. This substrate was subjected to ultrasonic cleaning for 5 minutes in isopropyl alcohol and further for 5 minutes in pure water, and then to UV ozone cleaning for 10 minutes using an apparatus manufactured by Samco International Laboratories. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Nippon Vacuum Technology Co., Ltd.), and N, N was attached to a molybdenum resistance heating boat.
Put 200 mg of N'-bis (3-methylphenyl) -N, N'-diphenyl [1,1'-biphenyl] -4,4'-diamine (TPD) and put it in a different molybdenum boat. Dimethyl-4,4'-bis (2,2-
200 mg of diphenylvinyl) biphenyl (DMDPVBi, ionization energy: 5.85 eV) was charged, and the pressure in the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa. Thereafter, the boat containing TPD is heated to 215 to 220 ° C., TPD is deposited on the transparent support substrate at a deposition rate of 0.1 to 0.3 nm / s, and a hole injection layer having a thickness of 60 nm is formed. Was. The substrate temperature at this time was room temperature. Without taking this out of the vacuum chamber, place the DM on the hole injection layer from another boat.
DPVBi was deposited to a thickness of 40 nm as a light emitting layer. The deposition conditions are as follows: boat temperature is 305 ° C and deposition rate is 0.1 to 0.3n.
m / s and the substrate temperature was room temperature. This was taken out of the vacuum chamber, a stainless steel mask was placed on the light emitting layer, and fixed again to the substrate holder. Next, 200 mg of tris (8-quinolinol) aluminum (Alq ₃ ) was put into a molybdenum boat, and the boat was attached to a vacuum chamber. Further, 1 g of a magnesium ribbon was placed in a molybdenum resistance heating boat, and 500 mg of silver wire was deposited in a different tungsten basket and vapor-deposited. Thereafter, the pressure in the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa, and the boat containing Alq ₃ was heated to 230 ° C. to reduce the volume of Alq ₃ from 0.01 to 0.0.
20 nm was deposited at a deposition rate of 3 nm / s. Furthermore, silver was simultaneously deposited at a deposition rate of 0.1 nm / s by a resistance heating method.
1.4n of magnesium from the other molybdenum boat
The deposition was started at a deposition rate of m / s. Under the above conditions, a mixed metal electrode of magnesium and silver was deposited to a thickness of 150 nm on the light emitting layer to form a counter electrode.

Example 7 ITO was placed on a glass substrate of 25 mm × 75 mm × 1.1 mm.
Was formed to a thickness of 100 nm by a vapor deposition method to obtain a transparent support substrate. This substrate was subjected to ultrasonic cleaning for 5 minutes in isopropyl alcohol and further for 5 minutes in pure water, and then to UV ozone cleaning for 10 minutes using an apparatus manufactured by Samco International Laboratories. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Nippon Vacuum Technology Co., Ltd.), and N, N was attached to a molybdenum resistance heating boat.
200 mg of N′-bis (3-methylphenyl) -N, N′-diphenyl [1,1′-biphenyl] -4,4′-diamine (TPD) was added, and obtained in a different molybdenum boat in Reference Example 7. Compound ((DPVTPVB)
i) ₂ E, ionization energy: 5.8eV) the 200m
g and the pressure in the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa. Thereafter, the boat containing TPD is heated to 215 to 220 ° C., TPD is deposited on the transparent support substrate at a deposition rate of 0.1 to 0.3 nm / s, and a hole injection layer having a thickness of 60 nm is formed. Was. The substrate temperature at this time was room temperature. This was taken out from the vacuum chamber, and (DPVTPVBi) ₂ E was used as a light-emitting layer on another hole-injecting layer.
nm. The deposition conditions were a boat temperature of 225 ° C., a deposition rate of 0.1 to 0.3 nm / s, and a substrate temperature of room temperature. This was taken out of the vacuum chamber, a stainless steel mask was placed on the light emitting layer, and fixed again to the substrate holder. Next, 200 mg of tris (8-quinolinol) aluminum (Alq ₃ ) was put into a molybdenum boat, and was deposited in a vacuum chamber. Further, 1 g of a magnesium ribbon was placed in a molybdenum resistance heating boat, and 500 mg of silver wire was deposited in a different tungsten basket and vapor-deposited. Thereafter, the pressure in the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa, and then the boat containing Alq ₃ was heated to 230 ° C.
Alq ₃ is deposited at a deposition rate of 0.01 to 0.03 nm / s for 20 n.
m was deposited. Further, silver was simultaneously deposited at a deposition rate of 0.1 nm / s by a resistance heating method and magnesium was deposited from the other molybdenum boat at a deposition rate of 1.4 nm / s. Under the above conditions, a mixed metal electrode of magnesium and silver was deposited to a thickness of 150 nm on the light emitting layer to form a counter electrode.

Example 8 ITO was placed on a 25 mm × 75 mm × 1.1 mm glass substrate.
Was formed to a thickness of 100 nm by vapor deposition.
It was a holding substrate. Put this substrate in isopropyl alcohol
Ultrasonic cleaning for 5 minutes in pure water for 5 minutes
Next, UV ozone cleaning was performed by Samco International
This was performed for 10 minutes using a device manufactured by Le Labs. This transparent support group
The plate was placed on a substrate evaporator (available from Nihon Vacuum Technology Co., Ltd.)
To the molybdenum resistance heating boat.
N'-bis (3-methylphenyl) -N, N'-dife
Nyl- (1,1'-biphenyl) -4,4'-diamine
(TPD) 200mg, another molybdenum bo
4,4'-bis (2,2'-diphenylvinyl)
200mg of biphenyl (DPVBi)
1 × 10^-FourThe pressure was reduced to Pa. After that, with TPD
The boat is heated to 215 to 220 ° C and the TPD is evaporated
Deposited on a transparent support substrate at a temperature of 0.1 to 0.3 nm / s to form a film
A hole injection layer having a thickness of 60 nm was formed. Substrate temperature at this time
The temperature was room temperature. Do not take this out of the vacuum chamber
On the hole injection layer, another boat (DPV
Bi) was deposited to a thickness of 40 nm as a light emitting layer. Deposition conditions
Means that the boat temperature is 240 ° C and the deposition rate is 0.1 to 0.3 nm /
s, The substrate temperature was room temperature. Take this out of the vacuum chamber
And put a stainless steel mask on the light emitting layer
It was set and fixed again to the substrate holder. Next molybdenum
Bis (8-hydroxyquinolinol) magne
Cium (Mg (Ox)_Two： Ionization energy 5.55e
V) was deposited in a vacuum chamber in an amount of 200 mg. In addition,
1g of magnesium ribbon in a resistance heating boat made of ribden
Put another silver basket in tungsten wire
Was deposited in an amount of 500 mg. After that, the vacuum tank is 1 × 1
0^-FourAfter reducing the pressure to Pa, Mg (Ox)_TwoBoss containing
Heat the sheet to 410 ° C and heat the Mg (Ox) _TwoFrom 0.01 to
20 nm was deposited at a deposition rate of 0.03 nm / s. Further
At the same time, silver was deposited at a deposition rate of 0.1 nm / s by resistance heating.
More magnesium from the other molybdenum boat
Deposition was started at a deposition rate of 1.4 nm / s. Under the above conditions,
A mixed metal electrode of gnesium and silver is placed on the light emitting layer for 150n.
m layers were deposited to form a counter electrode.

Example 9 ITO was placed on a 25 mm × 75 mm × 1.1 mm glass substrate.
Was formed to a thickness of 100 nm by vapor deposition.
It was a holding substrate. Put this substrate in isopropyl alcohol
Ultrasonic cleaning for 5 minutes in pure water for 5 minutes
Next, UV ozone cleaning was performed by Samco International
This was performed for 10 minutes using a device manufactured by Le Labs. This transparent support group
The plate was placed on a substrate evaporator (available from Nihon Vacuum Technology Co., Ltd.)
To the molybdenum resistance heating boat.
N'-bis (3-methylphenyl) -N, N'-dife
Nyl- (1,1'-biphenyl) -4,4'-diamine
(TPD) 200mg, another molybdenum bo
4,4'-bis (2,2'-diphenylvinyl)
200mg of biphenyl (DPVBi)
1 × 10^-FourThe pressure was reduced to Pa. After that, with TPD
The boat is heated to 215 to 220 ° C and the TPD is evaporated
Deposited on a transparent support substrate at a temperature of 0.1 to 0.3 nm / s to form a film
A hole injection layer having a thickness of 60 nm was formed. Substrate temperature at this time
The temperature was room temperature. Do not take this out of the vacuum chamber
On the hole injection layer, another boat (DPV
Bi) was deposited to a thickness of 40 nm as a light emitting layer. Deposition conditions
Means that the boat temperature is 240 ° C and the deposition rate is 0.1 to 0.3 nm /
s, The substrate temperature was room temperature. Take this out of the vacuum chamber
And put a stainless steel mask on the light emitting layer
It was set and fixed again to the substrate holder. Next molybdenum
Bis (8-hydroxyquinolinol) copper (C
uq_Two: 200 mg of ionization energy 5.45 eV)
It was then deposited in a vacuum chamber. In addition, molybdenum resistors
Put 1g magnesium ribbon in heated boat
500mg silver wire in tungsten basket
Deposited. After that, the vacuum chamber is 1 × 10^-FourDecompression to Pa
And then Cuq _TwoHeated boat to 480 ° C
And Cuq_TwoAt a deposition rate of 0.05 to 0.1 nm / s.
nm. Further, silver is deposited at a deposition rate of 0.1 nm / s.
At the same time, the other molybdenum boat
From magnesium at a deposition rate of 1.4 nm / s
I did. A mixed metal electrode of magnesium and silver is emitted under the above conditions.
A 150 nm layer was deposited on the optical layer to form a counter electrode.

Example 10 ITO was placed on a glass substrate of 25 mm × 75 mm × 1.1 mm.
Was formed to a thickness of 100 nm by vapor deposition.
It was a holding substrate. Put this substrate in isopropyl alcohol
Ultrasonic cleaning for 5 minutes in pure water for 5 minutes
Next, UV ozone cleaning was performed by Samco International
This was performed for 10 minutes using a device manufactured by Le Labs. This transparent support group
The plate was placed on a substrate evaporator (available from Nihon Vacuum Technology Co., Ltd.)
To the molybdenum resistance heating boat.
N'-bis (3-methylphenyl) -N, N'-dife
Nyl- (1,1'-biphenyl) -4,4'-diamine
(TPD) 200mg, another molybdenum bo
4,4'-bis (2,2'-diphenylvinyl)
200mg of biphenyl (DPVBi)
1 × 10^-FourThe pressure was reduced to Pa. After that, with TPD
The boat is heated to 215 to 220 ° C and the TPD is evaporated
Deposited on a transparent support substrate at a temperature of 0.1 to 0.3 nm / s to form a film
A hole injection layer having a thickness of 60 nm was formed. Substrate temperature at this time
The temperature was room temperature. Do not take this out of the vacuum chamber
On the hole injection layer, another boat (DPV
Bi) was deposited to a thickness of 40 nm as a light emitting layer. Deposition conditions
Means that the boat temperature is 240 ° C and the deposition rate is 0.1 to 0.3 nm /
s, The substrate temperature was room temperature. Take this out of the vacuum chamber
And put a stainless steel mask on the light emitting layer
It was set and fixed again to the substrate holder. Next molybdenum
Bis (8-hydroxyquinolinol) lead (P
bq_Two: 200 mg of ionization energy 5.45 eV)
It was then deposited in a vacuum chamber. In addition, molybdenum resistors
Put 1g magnesium ribbon in heated boat
500mg silver wire in tungsten basket
Deposited. After that, the vacuum chamber is 1 × 10^-FourDecompression to Pa
After that, Pbq _TwoThe boat with water to 290 ℃
And Pbq_TwoAt a deposition rate of 0.01 to 0.03 nm / s
0 nm was deposited. Further, silver is deposited at a deposition rate of 0.1 nm / s.
At the same time, the other molybdenum
Magnesium at a deposition rate of 1.4 nm / s
I started. Under the above conditions, a mixed metal electrode of magnesium and silver
A 150 nm layer was deposited on the light emitting layer to form a counter electrode.

Example 11 ITO was placed on a 25 mm × 75 mm × 1.1 mm glass substrate.
Was formed to a thickness of 100 nm by a vapor deposition method to obtain a transparent support substrate. This substrate was subjected to ultrasonic cleaning for 5 minutes in isopropyl alcohol and further for 5 minutes in pure water, and then to UV ozone cleaning for 10 minutes using an apparatus manufactured by Samco International Laboratories. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Nippon Vacuum Technology Co., Ltd.), and N, N was attached to a molybdenum resistance heating boat.
Put 200 mg of N'-bis (3-methylphenyl) -N, N'-diphenyl- (1,1'-biphenyl) -4,4'-diamine (TPD) and add 4,4 'to a different molybdenum boat -Bis (2,2'-diphenylvinyl)
200 mg of biphenyl (DPVBi) was charged, and the pressure in the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa. Thereafter, the boat containing TPD is heated to 215 to 220 ° C., TPD is deposited on the transparent support substrate at a deposition rate of 0.1 to 0.3 nm / s, and a hole injection layer having a thickness of 60 nm is formed. Was. The substrate temperature at this time was room temperature. This was taken out from another boat (DPV) on the hole injection layer without taking it out of the vacuum chamber.
Bi) was deposited to a thickness of 40 nm as a light emitting layer. The deposition conditions are as follows: boat temperature is 240 ° C., deposition rate is 0.1 to 0.3 nm /
s, The substrate temperature was room temperature. This was taken out of the vacuum chamber, a stainless steel mask was placed on the light emitting layer, and fixed again to the substrate holder. Then the boat made of molybdenum tris (8-hydroxy quinolinol) gallium (Gaq _3: ionization energy 5.5 eV) to 20
0 mg was deposited and deposited on a vacuum chamber. Furthermore, put 1g of magnesium ribbon in a molybdenum resistance heating boat, and put 500 silver wires in another tungsten basket.
mg was deposited. Thereafter, the pressure in the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa, and the boat containing Gaq ₃ was heated to 290 ° C., and Gaq ₃ was deposited at a deposition rate of 0.01 to 0.03 nm / s to a thickness of 20 nm. Further, silver was simultaneously deposited at a deposition rate of 0.1 nm / s by a resistance heating method and magnesium was deposited from the other molybdenum boat at a deposition rate of 1.4 nm / s. Under the above conditions, a mixed metal electrode of magnesium and silver was deposited to a thickness of 150 nm on the light emitting layer to form a counter electrode.

Example 12 ITO was placed on a glass substrate of 25 mm × 75 mm × 1.1 mm.
Was formed to a thickness of 100 nm by a vapor deposition method to obtain a transparent support substrate. This substrate was subjected to ultrasonic cleaning for 5 minutes in isopropyl alcohol and further for 5 minutes in pure water, and then to UV ozone cleaning for 10 minutes using an apparatus manufactured by Samco International Laboratories. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Nippon Vacuum Technology Co., Ltd.), and N, N was attached to a molybdenum resistance heating boat.
Put 200 mg of N'-bis (3-methylphenyl) -N, N'-diphenyl- (1,1'-biphenyl) -4,4'-diamine (TPD) and add 4,4 'to a different molybdenum boat -Bis (2,2'-diphenylvinyl)
200 mg of biphenyl (DPVBi) was charged, and the pressure in the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa. Thereafter, the boat containing TPD is heated to 215 to 220 ° C., TPD is deposited on the transparent support substrate at a deposition rate of 0.1 to 0.3 nm / s, and a hole injection layer having a thickness of 60 nm is formed. Was. The substrate temperature at this time was room temperature. This was taken out from another boat (DPV) on the hole injection layer without taking it out of the vacuum chamber.
Bi) was deposited to a thickness of 40 nm as a light emitting layer. The deposition conditions are as follows: boat temperature is 240 ° C., deposition rate is 0.1 to 0.3 nm /
s, The substrate temperature was room temperature. This was taken out of the vacuum chamber, a stainless steel mask was placed on the light emitting layer, and fixed again to the substrate holder. Next, 200 mg of tris (8-hydroxyquinolinol) indium (Inq ₃ : ionization energy 5.5 eV) was put into a boat made of molybdenum and vapor-deposited in a vacuum chamber. Further, 1 g of a magnesium ribbon was placed in a molybdenum resistance heating boat, and 500 mg of silver wire was deposited in a different tungsten basket and vapor-deposited. Thereafter, the vacuum chamber is set to 1 × 10 ^-4
After reducing the pressure to Pa, the boat containing Inq ₃
After heating to 5 ° C., Inq ₃ was deposited at a deposition rate of 0.01 to 0.03 nm / s to a thickness of 20 nm. Further, the silver was 0.1 nm /
At the same time, magnesium was vapor-deposited from the other molybdenum boat at a vapor deposition rate of 1.4 nm / s by the resistance heating method. Under the above conditions, a mixed metal electrode of magnesium and silver was deposited to a thickness of 150 nm on the light emitting layer to form a counter electrode.

Example 13 ITO was placed on a 25 mm × 75 mm × 1.1 mm glass substrate.
Was formed to a thickness of 100 nm by vapor deposition.
It was a holding substrate. Put this substrate in isopropyl alcohol
Ultrasonic cleaning for 5 minutes in pure water for 5 minutes
Next, UV ozone cleaning was performed by Samco International
This was performed for 10 minutes using a device manufactured by Le Labs. This transparent support group
The plate was placed on a substrate evaporator (available from Nihon Vacuum Technology Co., Ltd.)
To the molybdenum resistance heating boat.
N'-bis (3-methylphenyl) -N, N'-dife
Nyl- (1,1'-biphenyl) -4,4'-diamine
(TPD) 200mg, another molybdenum bo
4,4'-bis (2,2'-diphenylvinyl)
200mg of biphenyl (DPVBi)
1 × 10^-FourThe pressure was reduced to Pa. After that, with TPD
The boat is heated to 215 to 220 ° C and the TPD is evaporated
Deposited on a transparent support substrate at a temperature of 0.1 to 0.3 nm / s to form a film
A hole injection layer having a thickness of 60 nm was formed. Substrate temperature at this time
The temperature was room temperature. Do not take this out of the vacuum chamber
On the hole injection layer, another boat (DPV
Bi) was deposited to a thickness of 40 nm as a light emitting layer. Deposition conditions
Means that the boat temperature is 240 ° C and the deposition rate is 0.1 to 0.3 nm /
s, The substrate temperature was room temperature. Take this out of the vacuum chamber
And put a stainless steel mask on the light emitting layer
It was set and fixed again to the substrate holder. Next molybdenum
Tris (2-methyl-8-hydroxyquinolate)
Nord) Aluminum (Al (mq)_Three： Ionized energy
(5.55 eV) was deposited in a vacuum chamber.
Was. In addition, the resistance heating boat made of molybdenum
Um ribbon 1g, another tungsten basket
500 mg of a silver wire was put into the container and evaporated. afterwards,
1 × 10 vacuum chamber ^-FourAfter reducing the pressure to Pa,
q)_ThreeIs heated to 300 ° C., and Al (m
q)_ThreeAt a deposition rate of 0.01 to 0.03 nm / s to 20 nm
Evaporated. Further, silver was simultaneously deposited at a deposition rate of 0.1 nm / s.
From the other molybdenum boat by resistance heating
Start depositing magnesium at a deposition rate of 1.4 nm / s
Was. Light emission of mixed metal electrode of magnesium and silver under the above conditions
A 150 nm layer was deposited on the layer to form a counter electrode.

Example 14 ITO was placed on a glass substrate of 25 mm × 75 mm × 1.1 mm.
Was formed to a thickness of 100 nm by a vapor deposition method to obtain a transparent support substrate. This substrate was subjected to ultrasonic cleaning for 5 minutes in isopropyl alcohol and further for 5 minutes in pure water, and then to UV ozone cleaning for 10 minutes using an apparatus manufactured by Samco International Laboratories. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Nippon Vacuum Technology Co., Ltd.), and N, N was attached to a molybdenum resistance heating boat.
Put 200 mg of N'-bis (3-methylphenyl) -N, N'-diphenyl- (1,1'-biphenyl) -4,4'-diamine (TPD) and add 4,4 'to a different molybdenum boat -Bis (2,2'-diphenylvinyl)
200 mg of biphenyl (DPVBi) was charged, and the pressure in the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa. Thereafter, the boat containing TPD is heated to 215 to 220 ° C., TPD is deposited on the transparent support substrate at a deposition rate of 0.1 to 0.3 nm / s, and a hole injection layer having a thickness of 60 nm is formed. Was. The substrate temperature at this time was room temperature. This was taken out from another boat (DPV) on the hole injection layer without taking it out of the vacuum chamber.
Bi) was deposited to a thickness of 40 nm as a light emitting layer. The deposition conditions are as follows: boat temperature is 240 ° C., deposition rate is 0.1 to 0.3 nm /
s, The substrate temperature was room temperature. This was taken out of the vacuum chamber, a stainless steel mask was placed on the light emitting layer, and fixed again to the substrate holder. Next, 200 mg of tris (2-methyl-8-hydroxyquinolinol) indium (In (mq) ₃ : ionization energy 5.5 eV) was put into a boat made of molybdenum and vapor-deposited in a vacuum chamber.
Further, 1 g of a magnesium ribbon was placed in a molybdenum resistance heating boat, and 500 mg of silver wire was deposited in a different tungsten basket and vapor-deposited. Thereafter, the pressure in the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa, and then In (mq) ₃
Is heated to 315 ° C., and In (mq) ₃
Was deposited at a deposition rate of 0.01 to 0.03 nm / s by 20 nm. Further, silver was simultaneously deposited at a deposition rate of 0.1 nm / s by a resistance heating method and magnesium was deposited from the other molybdenum boat at a deposition rate of 1.4 nm / s. Under the above conditions, a mixed metal electrode of magnesium and silver was deposited to a thickness of 150 nm on the light emitting layer to form a counter electrode.

Comparative Examples 1 to 8 Except for once removing from the vacuum layer and installing again in the vacuum layer together with the boats of magnesium and silver, respectively, a mixed metal electrode of magnesium and silver was evaporated under the same conditions as in Example 1. An EL device was manufactured in the same manner as in Example 1.

Comparative Example 9 An EL device was manufactured in the same manner as in Example 2, except that the light emitting layer was 30 nm and the adhesive layer was 30 nm. The initial characteristics were as shown in Table 1.

[0093]

[Table 1]

Uniformity: 100 cd · m^-2To the brightness
Emit light and use a luminance meter (CS-100, Minolta Camera
Observation of the light-emitting surface using a
did. ×: No light emission area with a diameter of 10 μm or more in the observation area,
There is uneven color. ：: Uniform light emission in the observation area (no light emission area with a diameter of 10 μm or more)
Area or color unevenness). Efficiency: 100 cd · m^-2When the flash is fired at
2 shows the conversion efficiency. After performing this evaluation, these devices are subjected to I
With the TO as the anode and the metal electrode as the cathode, a DC electric field of 0 V /
from cm to 1.3 × 10⁶4.2 × 10 up to V / cm ^FourV / c
Apply for 2 seconds at m intervals, and measure the voltage-current characteristics.
Aging. In addition, the initial brightness in nitrogen
Degree 100cd ・ m^-2For 10 minutes.
The device thus treated is driven by DC current in nitrogen
, The initial luminance is 100 cd · m^-2Set to 24 hours
Continuous light emission was performed. Thereafter, the evaluation is performed using a luminance meter as described above.
Valued. In each of the embodiments, the light emission is uniform,
In Comparative Examples 1 to 8, the non-light-emitting area was enlarged, and in Comparative Example 9, color unevenness was observed.
Has grown. Table 2 shows the luminance at this time.

[0095]

[Table 2]

As described above, the example is the device configuration according to the claims of the present invention, and the comparative example is the device configuration excluding the adhesive layer. is there. It can be seen from the element configuration of the example that the luminous efficiency is improved and the deterioration is suppressed while the blue luminescence is maintained. Furthermore, comparing Example 2 and Comparative Example 9, it can be seen that it is efficient to make the thickness of the adhesive layer smaller than the thickness of the light emitting layer in order to maintain blue light emission.

[0097]

According to the organic EL device of the present invention, the in-plane uniformity of light emission can be improved, and at the same time, a decrease in the initial luminance can be suppressed, so that the device can be finely processed. , Improved yield, and a longer service life. Therefore, the organic EL device of the present invention is expected to be effectively used as various light emitting materials.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-247278 (JP, A) JP-A-2-222484 (JP, A) JP-A-2-209988 (JP, A) JP-A-2- 216790 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C09K 11/06 H05B 33/14

Claims (1)

(57) [Claims] An anode / light-emitting layer / adhesive layer / cathode, or
Anode / hole injection layer / light emitting layer / adhesive layer / cathode
Wherein the light emitting layer has the general formula (I):(Where R¹~ R^FourIs a hydrogen atom, and each has 1 to 6 carbon atoms
An alkyl group, an alkoxy group having 1 to 6 carbon atoms, 7 carbon atoms
~ 8 aralkyl groups, substituted or unsubstituted C6 ~
18 aryl groups, substituted or unsubstituted cyclohexyl
Group, substituted or unsubstituted aryl having 6 to 18 carbon atoms
It represents an oxy group or an alkoxy group having 1 to 6 carbon atoms. here
Wherein the substituent is an alkyl group having 1 to 6 carbon atoms,
An alkoxy group, an aralkyl group having 7 to 8 carbon atoms, a carbon number
6-18 aryloxy groups, C1-6 acyl
Group, an acyloxy group having 1 to 6 carbon atoms, a carboxyl group,
Styryl group, arylcarbonyl group having 6 to 20 carbon atoms,
Aryloxycarbonyl group having 6 to 20 carbon atoms, carbon number
1 to 6 alkoxycarbonyl groups, vinyl groups, anilino
Carbonyl group, carbamoyl group, phenyl group, nitro
Group, hydroxyl group or halogen. These substituents are
It may be single or plural. Also, R¹~ R^FourAre the same,
And may be different from each other;¹And R^TwoAnd R^Three
And R^FourIs bonded to the substituting group
Is an unsubstituted saturated 5-membered ring or a substituted or unsubstituted saturated
A member ring may be formed. Ar is a substituted or unsubstituted charcoal
Represents an aryl group having a prime number of 6 to 20, and is monosubstituted
Or a plurality of substituents, and the binding site is
Any of default, para, and meta may be used. However, Ar is unsubstituted
In the case of phenylene, R¹~ R^FourEach have 1 to 6 carbon atoms
An alkoxy group, an aralkyl group having 7 to 8 carbon atoms,
Or unsubstituted naphthyl, biphenyl, cyclohexyl
Selected from sil groups and aryloxy groups
You. ), General formula (II)(Wherein A and B are each represented by the above general formula (I)
A monovalent group obtained by removing one hydrogen atom from the compound
They may be the same or different. Q cuts the conjugate system.
A divalent group. ) Or general formula (III)(Where A¹Is a substituted or unsubstituted C 6-20
It represents an arylene group or a divalent aromatic heterocyclic group. Join
The position may be ortho, meta or para. A ^TwoIs
A substituted or unsubstituted aryl group having 6 to 20 carbon atoms or
And a monovalent aromatic heterocyclic group. R^FiveAnd R⁶Each
A hydrogen atom, a substituted or unsubstituted C 6-20
Aryl group, cyclohexyl group, monovalent aromatic heterocyclic
Group, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 7 to 20 carbon atoms.
It represents an aralkyl group or an alkoxy group having 1 to 10 carbon atoms.
Note that R^Five, R⁶May be the same or different. here,
Substituent means an alkyl group, an aryl
With or without xy, amino or substituent
It is a phenyl group. R^FiveEach substituent is A¹Combined with
May form a saturated or unsaturated 5- or 6-membered ring.
And likewise R⁶Each substituent is A^TwoCombined with
Alternatively, it may form an unsaturated 5- or 6-membered ring. Ma
Q represents a divalent group that cuts conjugation. )
From a compound that emits blue, green-blue or blue-green light.
The adhesive layer is 8-hydroxyquinoline or a derivative thereof
And the thickness of the light emitting layer
An organic electroluminescent device characterized by being thinner than the thickness.
Sense element. [0001]